Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene) n , n = 1,2

The S0 ↔ S1 spectra of the mild charge-transfer (CT) complexes perylene·tetrachloroethene (P·4ClE) and perylene·(tetrachloroethene)2 (P·(4ClE)2) are investigated by two-color resonant two-photon ionization (2C-R2PI) and dispersed fluorescence spectroscopy in supersonic jets. The S0 → S1 vibrationless transitions of P·4ClE and P·(4ClE)2 are shifted by δν = −451 and −858 cm–1 relative to perylene, translating to excited-state dissociation energy increases of 5.4 and 10.3 kJ/mol, respectively. The red shift is ∼30% larger than that of perylene·trans-1,2-dichloroethene; therefore, the increase in chlorination increases the excited-state stabilization and CT character of the interaction, but the electronic excitation remains largely confined to the perylene moiety. The 2C-R2PI and fluorescence spectra of P·4ClE exhibit strong progressions in the perylene intramolecular twist (1au) vibration (42 cm–1 in S0 and 55 cm–1 in S1), signaling that perylene deforms along its twist coordinate upon electronic excitation. The intermolecular stretching (Tz) and internal rotation (Rc) vibrations are weak; therefore, the P·4ClE intermolecular potential energy surface (IPES) changes little during the S0 ↔ S1 transition. The minimum-energy structures and inter- and intramolecular vibrational frequencies of P·4ClE and P·(4ClE)2 are calculated with the dispersion-corrected density functional theory (DFT) methods B97-D3, ωB97X-D, M06, and M06-2X and the spin-consistent-scaled (SCS) variant of the approximate second-order coupled-cluster method, SCS-CC2. All methods predict the global minima to be π-stacked centered coplanar structures with the long axis of tetrachloroethene rotated by τ ≈ 60° relative to the perylene long axis. The calculated binding energies are in the range of −D0 = 28–35 kJ/mol. A second minimum is predicted with τ ≈ 25°, with ∼1 kJ/mol smaller binding energy. Although both monomers are achiral, both the P·4ClE and P·(4ClE)2 complexes are chiral. The best agreement for adiabatic excitation energies and vibrational frequencies is observed for the ωB97X-D and M06-2X DFT methods.

Rede des Studenten Edmund Monecke bei seiner Verurtheilung in zweiter Instanz zu 2 1/2 Jahren Festungsstrafe und Verlust der National-Kokarde (im Juli 1848): Wenn man heute dem preußischen Volke das ruhige klare Auge eines Geschichtsforschers leihen könnte ...

Welsch (Projektbearbeiter): Rechtfertigung des Angeklagten gegen den Vorwurf der Majestätsbeleidigung

An analysis of the function of region 1.2 of the primary sigma factor, sigma 70, from Escherichia coli

The sigma (σ) subunit of eubacterial RNA polymerase is required for recognition of and transcription initiation from promoter DNA sequences. One family of sigma factors includes those related to the primary sigma factor from E. coli, σ70. Members of the σ70 family have four highly conserved domains, of which regions 2 through 4 are present in all members. Region 1 can be subdivided into regions 1.1 and 1.2. Region 1.1 affects DNA binding by σ 70 alone, as well as transcription initiation by holoenzyme. Region 1.2, present and highly conserved in most sigma factors, has not yet been assigned a putative function, although previous work demonstrated that it is not required for either association with the core subunits of RNA polymerase or promoter specific binding by holoenzyme. This study primarily investigates the functional role of region 1.2 during transcription initiation. In vivo and in vitro characterization of thirty-two single amino acid substitutions targeted to region 1.2 of E. coli σ70 as well as a deletion of region 1.2, revealed that mutations in region 1.2 can affect promoter binding, open complex formation, initiated complex formation, and the transition from abortive transcription to elongation. The relative degree of solvent exposure of several positions in region 1.2 has been determined, with positions 116 and 122 likely to be located near the surface of σ70. ^ During the course of this study, the existence of two “wild type” variants of E. coli σ70 was discovered. The identity of amino acid 149 has been reported variably as either arginine or aspartic acid in published articles and in online databases. In vivo and in vitro characterization of the two reported variations of E. coli σ70 (N149 and D149) has determined that the two variants are functionally equivalent. However, in vivo and in vitro characterization of single amino acid substitutions and a region 1.2 deletion in the context of each variant background revealed that the behavior of some mutations are greatly affected by the identity of amino acid 149. ^

Sterblichkeit der Juden in Wilna in den letzten 5 1/2 Jahren (1911-1916)

Zemach Schabad

Sterblichkeit der Juden in Wilna in den letzten 5 1/2 Jahren (1911-1916)

Zemach Schabad

[Bd 1/2]

Beide Bände in einem Digitalisat

Officielles un allein ächtes, in der kaiserlichen Hofdruckerei zu Bernem gedrucktes, Fest- & Krönungs-Programm : ... zur ... Krönung Seiner närrischen Majestät Kasier Carneval des Ersten in seiner alten & getreuen Närrischen Freien Reichs-, Krönungs- & Wahlstadt Frankfurt am Main an den Tagen und Nächten des 1., 2. und 3. des Martii, anno 1862

unverantwortlich verfasst von Fr. Stoltze

Inc. hebr. 1 Bd. 1/2 - Canon

Bei der Foliierung wurden Blätter übergangen, jetzt foliiert als Bl. 55a, 121a und 137a.

Inc. fragm. Speyer I Nr. 1 - Lectura super Sexto Decretalium. P.1.2

Rubriziert

Na 1 Nachlass Max Horkheimer, 622 - Unterlagen zu einführenden Vorlesungen (p. VIII 41,1-2-VIII 41b)

"Problem der neueren Philosophie", Vorlesung Wintersemester 1950/51 und Sommersemester 1951, 1) Heft, 78 Blatt und 20 zusätzliche Blätter, eigenhändige Notizen (GS 14, S. 145, 151-152), 2) Friedrich Pollock: Notizen zur Volesung Max Horkheimers, Wintersemester 1950/51), eigenhändige Notizen, 9 Blatt; "Philosophie im 17. Jahrhundert (insbes. Spinoza)", Vorlesung Winteremester 1951/52, 1) Heft 1, 17 Blatt und 2 zusätzliche Blätter, eigenhändige Notizen, 2) Heft 2, 46 Blatt, davon 3 leer, und 15 zusätzliche Blätter, eigenhändige Notizen; "Philosophie im 18. Jahrhundert", Vorlesung Sommersemester 1952, 1 Heft mit eigenhändigen Notizen, 64 Blatt, davon 30 leer, und 44 zusätzliche Blätter;

Na 1 Nachlass Max Horkheimer, 625 - Unterlagen zu den Vorlesungen "Einführung der Philosophie", "Geschichte des Materialismus" und "Society and Value" (p. VIII 42a-VIII 43,1-2)

"Einführung in die Philosophie", Vorlesung, Wintersemester 1956/57, 1 Heft mit eigenhändigen Notizen, 16 Blatt, davon 4 leer, mit 1 zusätzlichem Blatt; "Geschichte des Materialismus (ausgewählte Kapitel)" (GS 13, S. 397-451), Vorlesung, Sommersemester 1957, 1. Max Horkheimer, eigene Notizen, 1 Heft ohne Einband, 16 Blatt und 3 zusätzliche Blätter, 2. Hilmar Tillack: Ausgearbeitete Nachschrift der Vorlesung Max Horkheimers, Typoskript, 46 Blatt; "Society and Value", Vorlesung Chicago 1957, Heft 1: eigene Notizen, 60 Blatt, davon 13 leer, und zusätzliche 6 Blätter; Heft 2: eigene Notizen, 45 Blatt, davon 30 leer, und zusätzlich 8 Blatt; darin auch enthält: Begriff der Seele seit Leibniz", Vorlesung, Sommersemester 1958;

Na 1 Nachlass Max Horkheimer, 626 - Unterlagen zu den Vorlesungen "Society and Value" und "Die Idee der Freiheit" (p. VIII 43a-VIII 44,1-2)

"Society and Value", Vorlesung Chicago 1957, Heft 1: eigene Notizen, 60 Blatt, davon 13 leer, und zusätzlich 6 Blatt; Heft 2: eigene Notizen, 45 Blatt, davon 30 leer, und zusätzlich 8 Blätter. (Enthält auch: "Begriff der Seele seit Leibniz", Vorlesung Sommersemester 1958); "Die Idee der Freiheit" (GS 13, S. 452-514), Vorlesung Wintersemester 1957/58, eigene Notizen, 1 Heft, 45 Blatt, davon 23 leer, und zusätzlich 25 Blätter; Hilmar Tillack: Ausgearbeitete Nachschrift der Vorlesung Max Horkheimers, Typoskript, 58 Blatt;